CN101993169B - Treatment method of sintering flue gas desulphurization wastewater - Google Patents
Treatment method of sintering flue gas desulphurization wastewater Download PDFInfo
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- CN101993169B CN101993169B CN200910056567XA CN200910056567A CN101993169B CN 101993169 B CN101993169 B CN 101993169B CN 200910056567X A CN200910056567X A CN 200910056567XA CN 200910056567 A CN200910056567 A CN 200910056567A CN 101993169 B CN101993169 B CN 101993169B
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Abstract
The invention discloses a treatment method of sintering flue gas desulphurization wastewater, which completes the treatment on the sintering flue gas desulphurization wastewater through the following five steps of: 1. neutralization and coagulation: regulating the pH value of the sintering flue gas desulphurization wastewater to 8.5 to 9.5 by lye, and adding 0 to 200ppm of coagulating agents; 2. flocculation: adding 0 to 10ppm of coagulant aids for forming flocs; 3. precipitation and filter liquor separation; 4. biochemical treatment on filter liquor; and 5. deep treatment. The treatment method can be used for reducing the treatment cost of the desulphurization wastewater without generating influence on other treatment systems, thereby having good application and popularization prospects.
Description
Technical field
The invention belongs to the smelting iron and steel manufacture field, relate in particular to a kind of sintering flue gas desulfurization wastewater treatment method.
Background technology
Sintering process is atmospheric primary pollution source in China's smelting iron and steel operation, and the waste gas of being discharged shared ratio in whole Iron And Steel Plant is: flue dust 17%, SO2
46%, NO
X20%.The improvement of sinter fume becomes Iron And Steel Industry SO
2The emphasis that reduces discharging.In recent years, national environmental protection is to sintering device flue gas emission request also increasingly stringent: the national standard of issuing requires existing steel enterprise sintering machine SO
2Emission standard is 600mg/Nm
3, newly-built steel enterprise sintering machine emission standard in 2010 is 100mg/Nm
3
According to the national environmental protection planning requirement, the Eleventh Five-Year Plan period, non-electric industry such as iron and steel will form 300,000 tons of sweetening poweies.Sintering flue gas desulfurization is that steel industry is realized the key that sulfur dioxide pollution reduces discharging, and the situation is tense, and task is urgent.At present, thermoelectricity wins initial success through for many years desulfurized treatment, and sintering desulfuration will be the field of next keypoint treatment, also be the reduction of discharging focus and the difficult point of government and enterprises pay attention.
Throw huge fund abroad this has been administered, even closed sintering plant.Because some countries of Europe do not allow to produce sintering desulfuration waste water, and have specially in desuifurized disposal field, adopt dry desulfurization mostly, but are in the starting stage yet, still have many problems in the operational process.
The limestone-gypsum wet flue gas desulfurization is to use maximum, the most sophisticated sulfur removal technology of technology in the world, and this technology relatively is suitable for sintering flue gas desulfurization.Wet fuel gas desulfurizing technology can produce part waste water, i.e. desulfurization wastewater.For the flue gas desulfurization waste-water of power plant, relatively sophisticated treatment process is arranged, i.e. neutralization, sedimentation, flocculation, concentrating clarifying.For the sintering flue gas desulfurization system, China still is in the starting stage at present, does not also develop suitable sintering flue gas desulfurization waste water treatment process.
The water quality of sintering flue gas desulfurization waste water has substantial connection with the composition of the agglomerate that is adopted, so the desulfurization waste water quality difference of each sintering plant is bigger.Generally speaking, sintering flue gas desulfurization waste water and means of flue gas desulfurization of power plant waste water have certain similarity, but also difference to some extent.Two kinds of desulfurization wastewaters all are slightly acidic, and pH generally between 5 ~ 6, contains a large amount of suspended substance (being mainly gypsum particle), fluorion and trace heavy metals ion, like Pb, Cd, Zn, Hg etc. simultaneously; The concentration of fluorion generally is no more than discharging standards in the sintering flue gas desulfurization waste water; Therefore need not carry out defluorination; The concentration of heavy metal ion is also high than power plant desulfurization waste water in addition, and the kind of heavy metal ion changes with the variation of agglomerate composition, both maximum differences be exactly in the sintering flue gas desulfurization waste water ammonia nitrogen content very high; And rangeability is very big; Ammonia nitrogen in certain factory's sintering flue gas desulfurization waste water is 45-900mg/L, and average 420mg/L does not then contain ammonia nitrogen in the means of flue gas desulfurization of power plant waste water.The technology that the means of flue gas desulfurization of power plant wastewater treatment is adopted does not usually have the ammonia nitrogen removal function, so the desulfurization wastewater treatment process of power plant can not satisfy the needs of sintering flue gas desulfurization wastewater treatment.
For ammonia nitrogen waste water, the treatment process that can adopt has blow-off method, break point chlorination, chemical precipitation method and biological denitrificaion method etc.
It is to utilize free ammonia (NH that blow-off method is removed ammonia nitrogen
3) and ammonium ion (NH
4+) between running balance, through adjustment pH, ammonia nitrogen is mainly existed with the free ammonia form, and then carries out aeration stripping, free ammonia is overflowed from water, thereby reaches the purpose of removing ammonia nitrogen.Research needs adjustment pH＞12 if ammonia nitrogen removal frank is reached more than 90%, and therefore temperature＞90 ℃ can only adopt steam or warm air stripping, and will make discharged wastewater met the national standard, also need increase other subsequent treatment process.This technology has following shortcoming: 1. cost for wastewater treatment is than higher; The free ammonia of 2. overflowing can cause secondary pollution; 3. water temperature reduces, and the deamination effect also decreases.
It is that chlorine or Youxiaolin are dropped into waste water that break point chlorination is removed ammonia nitrogen, the ammonia nitrogen in the waste water is oxidized to the chemical denitrification process of nitrogen.This technology generally only is used for the ammonia nitrogen waste water of lower concentration and handles.
It is compound and phosphoric acid or hydrophosphate through in waste water, adding magnesium that chemical precipitation method is removed ammonia nitrogen, generates magnesium ammonium phosphate sediment, thereby removes the ammonia nitrogen in the waste water.The molecular formula of magnesium ammonium phosphate is MgNH
4PO
46H
2O is commonly called as struvite, can be used as the additive of compost, garden soil or the fire retardant chemical of building structure goods.It is simple that this method has technology, do not receive advantages such as temperature limitation, but the reagent consumption amount is big, and processing cost is high, and ammonia-N removal rate is at 70-80%, and the ammonia nitrogen after the processing can not satisfy emission standard, also needs further to handle.
The biological denitrificaion method is to utilize action of microorganisms to remove ammonia nitrogen; At first nitrifier is converted into nitric nitrogen with ammonia nitrogen under aerobic condition; Then nitrification liquid is back in the anoxic pond and under the effect of denitrifying bacteria, nitre nitrogen is reduced to nitrogen, thoroughly remove the nitrogen in the waste water.Biological process is low owing to having processing cost, does not have advantages such as secondary pollution, thereby is widely used in field of waste water treatment.But biological treatment has certain requirement to water quality, comprise the necessary nutritive element of microorganism growth (like a certain proportion of carbon, nitrogen, phosphorus etc.), suitable pH, and do not contain the virulent material of biological growth (like heavy metal ion etc.).Do not have the required carbon source of microorganism growth in the sintering flue gas desulfurization waste water, therefore be not suitable for adopting separately biological treatment.
Coking chemical waste water also is a kind of high ammonia-nitrogen wastewater, contains the required organism of microorganism growth simultaneously.The treatment process that coking chemical waste water adopts biological process to combine with physico-chemical process usually.In recent years, A/A/O in the biological treatment (anaerobism, anoxic and aerobic, first alphabetical abbreviation of English Anaerobic-Anoxic-Oxic) and A/O (anoxic and first alphabetical abbreviation of aerobic English Anoxic-Oxic) process application are comparatively extensive.Owing to contain a large amount of refractory organics in the coking chemical waste water; Biological treatment generally can not reach emission standard; Need carry out advanced treatment with further removal COD and colourity, adopt technologies such as coagulating sedimentation, chemical oxidation, filtration, charcoal absorption and ultrafiltration usually.
Consult existing patent and documents and materials, also be not directed against the report of sintering flue gas desulfurization waste water treatment process aspect at present.
Summary of the invention
The purpose of this invention is to provide a kind of sintering flue gas desulfurization wastewater treatment method, can be according to the water quality and quantity situation of sintering flue gas desulfurization waste water, in conjunction with the particular case of steel industry, develop economy, sintering flue gas desulfurization method of wastewater treatment efficiently.
The objective of the invention is to realize like this: a kind of sintering flue gas desulfurization wastewater treatment method comprises following steps:
1) neutralization, coagulation: through alkali lye the pH value of sintering flue gas desulfurization waste water is adjusted to 8.5-9.5, dosing coagulant, the amount of coagulating agent is 0-200ppm;
2) flocculation: add coagulant aids, the amount of coagulant aids is 0-10ppm;
3) deposition is isolated filtrating;
4) filtrating is carried out biochemical treatment;
5) carry out advanced treatment again.
Preferably, the alkali lye in the said step 1) is calcium hydroxide or sodium hydroxide.
Preferably, the coagulating agent in the said step 1) is one or more in iron trichloride, ferric sulfate, ferrous sulfate, aluminum chloride, Tai-Ace S 150, bodied ferric sulfate, Poly aluminum Chloride (PAC), the polymeric aluminium ferrum silicate.
In sintering flue gas desulfurization waste water, add alkali lye; Alkali lye can adopt calcium hydroxide or sodium hydroxide; With the pH regulator of waste water to 8.5-9.5; The while dosing coagulant, coagulating agent can adopt iron trichloride, ferric sulfate, ferrous sulfate, aluminum chloride, Tai-Ace S 150, bodied ferric sulfate, Poly aluminum Chloride (PAC), polymeric aluminium ferrum silicate etc., dosage 0-200ppm.
Preferably, coagulant aids is a SEPIGEL 305 said step 2).
Stir at a slow speed in the flocculation basin, add coagulant aids simultaneously, like SEPIGEL 305 etc., dosage 0-10ppm makes colloidal solid and suspended particle that cohesion take place and assembles, and forms bigger flco, from liquid phase, separates.
The water outlet of flocculation basin gets into settling tank, at this mud-water separation takes place, and suspended substance and heavy metal ion are able to remove.Throw out is deposited on the bottom and is condensed into mud, and top then is treat effluent.The mud that settling pond is discharged is after the pressure filter dehydration, and the mud cake outward transport is filtrated and returned neutralization tank.
Preferably, said step 4) mesophytization is handled, and filtrating is mixed with coking chemical waste water, and wherein the ratio of filtrating is no more than 15%.
Preferably, said step 4) mesophytization is treated to anoxic and aerobic or anaerobism, anoxic and aerobic biochemical reaction.
The water outlet of settling tank is delivered to the equalizing tank of coking wastewater processing system, and filtrating is mixed with coking chemical waste water, and wherein the ratio of filtrating is no more than 15%, gets into the A/O or the A/A/O biochemical treatment of coking chemical waste water.
Preferably, the advanced treatment in the said step 5) is one or more in coagulating sedimentation, chemical oxidation, filtration, charcoal absorption and the ultrafiltration technology.
The present invention makes it compared with prior art owing to adopted above technical scheme, has the following advantages and positively effect:
All there is the coke-oven plant of oneself in most of iron and steel enterprises, and the coke-oven plant mostly is provided with perfect Treatment of Coking Effluent facility.Compare with the water yield of coking chemical waste water, the water yield of sintering flue gas desulfurization waste water seldom, its ratio is less than 10% of coking chemical waste water.And organic concentration is very low in the desulfurization wastewater, and can play certain diluting effect to organism in the coking chemical waste water and poisonous and hazardous prussiate etc. after coking chemical waste water mixes.After sintering flue gas desulfurization waste water and coking chemical waste water combination treatment, the processing cost of desulfurization wastewater reduces than individual curing greatly, just neutralization, coagulation, sedimentary treatment facility and working cost.And for coking wastewater processing system, because the principal pollutant of blended desulfurization wastewater have only ammonia nitrogen, and the water yield is very little, can not exert an influence to its treatment system.
Embodiment
Embodiment 1:
Contain a large amount of suspended substances and trace heavy metals ion in the sintering flue gas desulfurization waste water, before getting into the biochemical treatment system of coking chemical waste water, need neutralize, coagulation, precipitation process.Reaction conditions is: adds aqua calcis the pH of desulfurization wastewater is adjusted to 8.5, add the SEPIGEL 305 of 10ppm, and reaction 30min postprecipitation, the sintering flue gas desulfurization waste water quality before and after handling is as shown in table 1.Can see that after neutralization, coagulation, precipitation process, heavy metal ion all reaches national grade one discharge standard, ammonia-N removal rate is very low, has only 3.8%.
The neutralization of table 1 sintering flue gas desulfurization waste water, sedimentation effect
Embodiment 2:
Neutralization, coagulation, sedimentary reaction conditions are: add aqua calcis the pH of desulfurization wastewater is adjusted to 9; Add the bodied ferric sulfate of 30ppm and the SEPIGEL 305 of 1ppm simultaneously; Reaction 30min postprecipitation, the sintering flue gas desulfurization waste water quality before and after handling is as shown in table 2.Can see that after neutralization, coagulation, precipitation process, heavy metal ion all reaches national grade one discharge standard, ammonia-N removal rate is 8.2%.
The neutralization of table 2 sintering flue gas desulfurization waste water, sedimentation effect
Embodiment 3:
Neutralization, coagulation, sedimentary reaction conditions are: add aqua calcis the pH of desulfurization wastewater be adjusted to 9.5, add the bodied ferric sulfate of 200ppm simultaneously, and reaction 30min postprecipitation, the sintering flue gas desulfurization waste water quality before and after handling is as shown in table 3.Can see that after neutralization, coagulation, precipitation process, heavy metal ion all reaches national grade one discharge standard, ammonia-N removal rate reaches 16%.
The neutralization of table 3 sintering flue gas desulfurization waste water, sedimentation effect
Embodiment 4:
Neutralization, sintering flue gas desulfurization waste water and coking chemical waste water after the precipitation process according to 1: 9 mixed, are got into the A/A/O biochemical treatment system afterwards.The reaction conditions of biochemical system is: the hydraulic detention time 50h of system, wherein the hydraulic detention time of anaerobism section, anoxic and aerobic section is respectively 10h, 13.3h and 26.7h.The treatment effect that adds sintering flue gas desulfurization waste water front and back biochemical treatment system is as shown in table 4.Can see by data in the table because that the water quality of coking chemical waste water itself changes is bigger, add desulfurization wastewater after, the water quality of composite waste and coking chemical waste water are unobvious to be distinguished; Removal effect to COD, TOC, TN and ammonia nitrogen does not have tangible difference yet, therefore, adds 10% sintering flue gas desulfurization waste water in the coking chemical waste water and can not impact the existing treatment system of coking chemical waste water.
Table 4 adds the removal effect of desulfurization wastewater (10%) front and back to each contamination index
Embodiment 5
Neutralization, sintering flue gas desulfurization waste water and coking chemical waste water after the precipitation process according to 1.5: 8.5 mixed, are got into the A/A/O biochemical treatment system afterwards.The reaction conditions of biochemical system is: the hydraulic detention time 50h of system, wherein the hydraulic detention time of anaerobism section, anoxic and aerobic section is respectively 10h, 13.3h and 26.7h.The treatment effect that adds sintering flue gas desulfurization waste water front and back biochemical treatment system is as shown in table 5.Can see by data in the table, the ratio of desulfurization wastewater is increased to 15% after, the TOC and the COD of composite waste slightly reduce, the concentration of ammonia nitrogen and total nitrogen slightly increases; But system does not have tangible difference to the removal effect of COD, TOC, ammonia nitrogen and total nitrogen.Therefore, adding 15% sintering flue gas desulfurization waste water in the coking chemical waste water can not impact the existing treatment system of coking chemical waste water.
Table 5 adds the removal effect of desulfurization wastewater (15%) front and back to each contamination index
Embodiment 6
Neutralization, sintering flue gas desulfurization waste water and coking chemical waste water after the precipitation process according to 2: 8 mixed, are got into the A/A/O biochemical treatment system afterwards.The reaction conditions of biochemical system is: the hydraulic detention time 50h of system, wherein the hydraulic detention time of anaerobism section, anoxic and aerobic section is respectively 10h, 13.3h and 26.7h.The treatment effect that adds sintering flue gas desulfurization waste water front and back biochemical treatment system is as shown in table 6.Can see by data in the table, the ratio of desulfurization wastewater is increased to 20% after, the TOC and the COD of composite waste slightly reduce, the concentration of ammonia nitrogen and total nitrogen increases to some extent; But system does not have tangible difference to the removal effect of COD, TOC and ammonia nitrogen, but because the carbon source concentration reduction, and total nitrogen concentration increases, so nitrogen removal rate decreases.
Table 6 adds the removal effect of desulfurization wastewater (20%) front and back to each contamination index
In sum; The present invention with sintering flue gas desulfurization waste water and coking chemical waste water combination treatment after, reduced production cost, and for coking wastewater processing system; Because the principal pollutant of blended desulfurization wastewater have only ammonia nitrogen; And the water yield is very little, can not exert an influence to its treatment system, thereby possess good prospect for promotion and application.
Be noted that above enumerate be merely several specific embodiment of the present invention, obviously the invention is not restricted to above embodiment, many similar variations are arranged thereupon.If those skilled in the art all should belong to protection scope of the present invention from all distortion that content disclosed by the invention directly derives or associates.
Claims (8)
1. sintering flue gas desulfurization wastewater treatment method is characterized in that comprising following steps:
1) neutralization, coagulation: through alkali lye the pH value of sintering flue gas desulfurization waste water is adjusted to 8.5-9.5, dosing coagulant, the amount of coagulating agent is 0-200ppm;
2) flocculation: add coagulant aids, form flco, the amount of coagulant aids is 0-10ppm;
3) deposition is isolated filtrating;
4) will filtrate to mix with coking chemical waste water and carry out biochemical treatment, wherein the ratio of filtrating is no more than 15%;
5) carry out advanced treatment again.
2. sintering flue gas desulfurization wastewater treatment method as claimed in claim 1 is characterized in that: the alkali lye in the said step 1) is calcium hydroxide.
3. sintering flue gas desulfurization wastewater treatment method as claimed in claim 1 is characterized in that: the alkali lye in the said step 1) is sodium hydroxide.
4. sintering flue gas desulfurization wastewater treatment method as claimed in claim 1 is characterized in that: the coagulating agent in the said step 1) is one or more in iron trichloride, ferric sulfate, ferrous sulfate, aluminum chloride, Tai-Ace S 150, bodied ferric sulfate, Poly aluminum Chloride (PAC), the polymeric aluminium ferrum silicate.
5. sintering flue gas desulfurization wastewater treatment method as claimed in claim 1 is characterized in that: coagulant aids is a SEPIGEL 305 said step 2).
6. sintering flue gas desulfurization wastewater treatment method as claimed in claim 1 is characterized in that: said step 4) mesophytization is treated to anoxic and aerobic biochemical reaction.
7. sintering flue gas desulfurization wastewater treatment method as claimed in claim 1 is characterized in that: said step 4) mesophytization is treated to anaerobism, anoxic and aerobic biochemical reaction.
8. sintering flue gas desulfurization wastewater treatment method as claimed in claim 1 is characterized in that: the advanced treatment in the said step 5) is one or more in coagulating sedimentation, chemical oxidation, filtration, charcoal absorption and the ultrafiltration technology.
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